Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
  • H01B3/305—Polyamides or polyesteramides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
  • H01B3/306—Polyimides or polyesterimides
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0346—Organic insulating material consisting of one material containing N

Definitions

• This invention relates to modificed imide resins with improved heat resistance and/or flexural strength.
• the conventional known polyamide imide resins exhibit excellent electrical characteristics, heat resistance and mechanical properties and are therefore used for electrical insulating varnishes and heat resistant films and sheets. It is desired that films of sheets for printed circuit boards, for example, be capable of withstanding a soldering bath at 260 to 280°C.
• the polyamide imide resins commercially available at present still have to be improved as to heat resistance in such a soldering bath.
• the carboxyl groups when condensed with N-methylolated methacryl- or acryl-amide, permit the highly reactive acryloyl groups to cross-link with each other more easily without entailing a reduction in the molecular weight of the cross linked portion. This makes it possible to impart improved heat resistance to the resin without deteriorating its flexural strength.
• useful polyamide imide resins are those having carboxyl groups.
• Such resins can be prepared by various processes.
• the polyamide imides prepared from polybasic acid anhydrides and diisocyanates those produced from aromatic polybasic acid anhydrides and aromatic diisocyanates are preferred especially for ensuring improved heat resistance.
• a suitable resin can be prepared by reacting excess trimellitic anhydride with an aromatic diisocyanate at 50 to 200°C for several hours. In this case, it is preferred to use 1.0 to 1.2 moles of trimellitic anhydride per mole of the diisocyanate.
• polyamide imide resins having carboxylic groups it is generally convenient to use a mixture of an aromatic diisocyanate as diisocyanate and an aromatic tribasic acid anhydride as polybasic acid anhydride. If desired, this mixture/-also contain an aromatic tetrabasic acid anhydride as further polybasic acid anhydride. This yields resins having good heat resistance.
• aromatic diisocyanates examples include toluylene diisocyanate, diphenylmethane diisocyanate, diphenylether diisocyanate, etc., which are used alone or in admixture.
• useful aromatic polybasic acid anhydrides are trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc..
• trimellitic anhydride Since the use of at least 50 mole % of trimellitic anhydride affords good results as regards solubility of the polyamide imide resins, it is preferred to use the tetracarboxylic acid anhydride, preferably pyromellitic anhydride or benzophenone-tetracarboxylic anhydride in an amount of up to 50 mole %, more preferably of 0 to 40 mole %, based on the total polybasic acid anhydride employed.
• the polycondensation reaction is conducted in the persence of a solvent.
• solvents examples include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric amide, N-methyl-pyrrolidone and similar aprotic polar solvents. These solvents can be used alone or in admixture. Aromatic hydrocarbons and ketones can also be used together- with such solvents insofar as the polyamide imide resin does not precipitate.
• the polycondensation reaction is preferably carried out at a temperature of 50 to 200°C, more preferably at 100 to 180°C,
• the carboxyl groups in the resulting polyamide imide resins are quantitatively determined by potentiometric titration with sodium methylate.
• the polyamide imide resins thus obtained contain at least four carboxyl groups per molecule. Although resins containing a smaller number of carboxyl groups can be used they will not be modified effectively with N-methylolated methacryl- or acryl- amides or derivatives thereof.
• N-methylolated methacryl- or acryl-amide or derivatives thereof are used preferably in an amount of about 1.0 to about 5.0 mole equivalent weights, more preferably of about 1.0 to about 2.0 mole equivalent weights, per mole equivalent weight of carboxyl groups.
• Examples of useful amides are N-methylolated acrylamide, N-alkoxymethyl acrylamides, preferably n-alkoxy (C 1 to C 4 ) methyl acrylamides such as N-methoxymethyl acryl- amide, N-ethoxymethyl acrylamide, N-propoxymethyl acryl- amide, and N-butoxymethyl acrylamide, and N-methylolated methacrylamide, N-alkoxymethyl methacrylamides, preferably N-alkoxy (C 1 to C 4 ) methyl methacrylamide such as N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide N-propoxymethyl methacrylamide, and N-butoxymethyl methacrylamide.
• the polyamide imide having carboxyl groups is reacted with an N-methylolated methacryl-or acryl-amide or a derivative thereof at a temperature of 50 to 200°C, preferably 100 to 150°C for 0.5 to 3 hours.
• a temperature of 50 to 200°C preferably 100 to 150°C for 0.5 to 3 hours.
• amide compounds in the reaction system are likely to polymerize. Satisfactory results can be achieved if the reaction is effected in the presence of 5 to 200 ppm of a polymerization inhibitor such as BHT.
• the modified polyamide imide resins obtained can be cured or polymerized by a radical mechanism and possess improved heat resistance and also enhanced flexural strength as compared with the original resin.
• resins of further improved heat resistance can be obtained by adding a bismaleimide compound of the formula and their derivates, wherein X ix CH 2 ,,0, S0 2 , S, or C( CH 3 ) 2 and their derivatives to the above reaction system for further modification.
• the bismaleimide compounds can be used in admixture with the N-methylolated methacryl- or acryl-amides or derivatives thereof, and the polyamide imide resin to be modified, or can be added to the reaction mixture of polyamide imide resin modified with N-methylolated methacryl- or acryl-amide or a derivative. This finding has led to another feature of the invention.
• the bismaleimides are used preferably in an amount of 5 to 50 % by weight based on the polyamide imide resin. Less than 5 % by weight of the bismaleimide will not result in sufficiently improved heat resistance, whereas the use of more than 50 % by weight of the compound gives films of impaired flexural strength.
• azobisisobutyronitrile azo- bisvaleronitrile or similar azo compounds
• di- tert.-butyl peroxide benzoyl peroxide or similar peroxides can be added as radical initiators to the inventive resins for curing or further polymerization.
• benzoyl peroxide or similar peroxides can be added as radical initiators to the inventive resins for curing or further polymerization.
• films or sheetings are formed at a temperature not lower than 150°C
• the desired shaped articles can be obtained merely by heating the resin in the absence of a radical initiator.
• modified polyamide imide resins of the invention may contain further additives, depending on the final use of the resins.
• polyamide imide resin I 0.95 mole of diphenylmethane diisocyanate (MDI) and 1.00 mole of trimellitic anhydride were placed into a 2- liter three-necked flask. The air in the flask was replaced by nitrogen, and 1200 ml of N-methyl-2-pyrrolidone were charged into the flask. The mixture was reacted at 100°C for 1.5 hours, at 130°C for 2 hours and further at 180°C for 6 hours under stirring.
• MDI diphenylmethane diisocyanate
• trimellitic anhydride 1200 ml
• the solution of the polyamide imide resin in N-methyl-2-pyrroldione had a viscosity of 2,000 centipoises at room temperature.
• polyamide imide resin II 1.02 mole of diphenylmethane diisocyanate and 1.00 mole of trimellitic anhydride were placed into a 2-liter three-necked flask. The air in the flask was replaced by nitrogen, and 1200 ml of N-methyl-2-pyrrolidone were charged into the flask. The mixture was reacted at 100°C for 1 hour, at 130°C for 2 hours and further at 180°C for 4 hours. Subsequently 0.04 mole of pyromellitic anhydride was added to the mixtrue, and the resulting mixture was reacted at 130°C for 2 hours.
• a solution of the polyamide imide resin in N-methyl-2-pyrrolidone had a viscosity of 14,000 centipoises at room temperature.
• N-methylolated acrylamide was added to the solution of the polyamide imide resin I, and the mixture was treated in the presence of 10 ppm of BHT at 120°C for 1 hour and thereafter cooled.
• Benzoyl peroxide (2 % by weight) was added to the resulting mixture, and the resin solution obtained was applied to a glass plate.
• the coated plate was heated to 180 - 280°C over a period of 30 minutes to prepare a film.
• examples 2 and 3 the above procedure was repeated, respectively using the polyamide imide resin II solution and a commercial polyamide imide resin (trademark "HI-400", product of Hitachi Kasei Co., Ltd., Japan, 6,000 centipoises at room temperature).
• HI-400 commercial polyamide imide resin
• the films were all 50 ⁇ thick.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)

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• 1979
  • 1979-07-13 JP JP8962679A patent/JPS5614554A/ja active Granted
• 1980
  • 1980-07-09 US US06/167,335 patent/US4387192A/en not_active Expired - Lifetime
  • 1980-07-11 EP EP80104023A patent/EP0023610B1/de not_active Expired
  • 1980-07-11 DE DE8080104023T patent/DE3066584D1/de not_active Expired
• 1982
  • 1982-12-23 US US06/452,432 patent/US4451621A/en not_active Expired - Lifetime

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